Polymeric partial esters of hydrocarbon-diimidazolinylalkanols and dicarboxylic acids



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Patented June 6, 1961 POLYMERIC PARTIAL ESTERS F HYDRO- CARBON-DIIMIDAZOLINYLALKANOLS AND DICARBOXYLIC ACIDS William B. Hughes, Webster Groves, and Verner -"Stromberg,'-Shr ewsbury, Mo., assignors to Petrohte Corporation, Wilmington, Del, a corporation of Dela! ware r r a No Drawing. Filed Mar. 3, 1958, Ser. No. 718,489 3 Claims. (Cl. 260 309.6)

acid so that at least one of the carboxylic acid groups remains unesterified, This invention also relates to a process of using these partial esters as corrosive inhibitors in preventing the corrosion of metals, most particularly iron, steel and ferrous alloys.

Heretofore, a wide variety of cyclic amidine compounds have been employed to inhibit the corrosion of oil well equipment. Although we have expected that hydroxyaliphatic cyclic amidines would also be effective in inhibiting oil field corrosion, We found that these comp u d h y p o co rosio i ting p pe i However, we have now unexpectedly discovered that certain derivatives of these hydroxyaliphatic cyclic amidines, particularly the partial esters thereof, are very-eta fective corrosion inhibitors, in many cases from to and =C--R+C,= are the residual ra icals derived from thecarboxylic acids:

0 Ba i-0n or R-(iiou),

where R comprises, for example, a saturated or unsaturated aliphatic radical, a cycloaliphaticradical, an aryl o mor t m s as refl tiv a h c r po di .hY LQ Yr aliphatic cyclic amidine. The corrosion inhibitors disclosed herein are particularly useful .in preventing the corrosion of oil well equipment, for example, in producing wells, pipe linearefinerie's, tank storage, etc., which are in contact with'cor-rosive oil-containing medium, for example, in oil wells producing corrosive oil or oil-brine mixtures in refineries, and the like. These compositions possess properties which impart to metals resistance to attack by a Wide variety of corrosive agents, among which may be mentioned brines, 'organic and inorganic acids, CO H 0, 0 etc., and combinations thereof.

, More specifically, the above'described compounds may be described by the formulae:

(1) A N N R' radical, an aralkyl radical, an alkaryl radical, an alkoxyalkyl radical, an aryloxyalkyl radical, and the like; and A is anaikylene group, for example, ethylene and propylent radicals have a main chain of 2 or 3 carbon atoms, Such. as ,C 2 2* -C 2 2 HP n on, on, on;

and x is a hol numb 1 o e e Q a e 1-2 n R s 9 Pa t a es e oup de v o t sa o a .h d o y spma n lk a i po wsyal ylsn groups with less than a stoichiometric amount of the polycarboxylic acid,

0 -a, th R nta s a least OHQIgjTQ 29 materials with oxygen, and combinations of said materials with each other and oxygen, which comprises treating such ferrous metals such as by adding to said fluids at least 5 parts per million of the above partial esters, said compounds being sufiiciently soluble in the hydrocarbon fluid to inhibit corrosion,

THE HYDROXY ALIPHATICYCLIC AMIDINE The expression ,cyclic amidines is employed in its usual sense to indicate ring compounds in which there are present either 5 or 6 members, and having Znitrogen atoms separated by a single carbon atom supplemented by either two additional carbon atoms or three additional carbon atoms completing the ring. All the carbon atoms may be substituted. In the present instance the nitrogen atom of the ring involving two monovalent linkages (the 1-position) is substituted with a hydroxy aliphatic group, i.e., ,'(RO)nH group when R is alkylene and n is a whole number, for example, 1-5 or higher.

These cyclic amidines are further characterized as being substituted imidazolines and tetrahydropyrimidines in-which the two-position carbon of the ring is generally bonded to a hydrocarbon radical or comparable radical derived from an acid such as a low nolal-fatty acid, a

high molal fatty acid, or. comparable acids, polycarboxy I acids, and the like.

For details of the preparation of imidazolines substituted in the 2-position from amines, see the following US. patents, US. No. 1,999,989, dated April 30, 1935, Max Bockmuhl et al.; U.S. No. 2,155,877, dated April 25, 1939, Edmund Waldmann et al.; and US. No. 2,155,878, dated April 25, 1939, Edmund Waldmann et al. Also see Chem. Rev. 32, 47 (43), and Chem. Rev. 54, 593 (54) Equally suitable for use in preparing compounds useful in our invention and for the preparation of tetrahydropyrimidines substituted in the 2-position are the corresponding polyamines containing at least one primary amino group and one secondary amino group, or another primary amino group separated from the first primary amino group by three carbon atoms instead of being separated by only 2 carbons as with imidazolines. This reaction as in the-case of the imidazoline is generally carried out by heating the reactants to-a temperature at which 2 moles of water are evolved and ring closure is efiected. For details of the preparation of tetrahydropyrimidines, see German Patent No. 700,371, dated December 18, 1940, to Edmund Waldmann and August Chwala; German Patent No. 701,322, dated January 14, 1941, to Karl Kiescher, Ernst Urech and Willi Klarenand U.S. Patent No. 2,194,419, dated March 19, 1940, to

August Chwala. Substituted imidazoliries and tetrahydropyrimidines are obtained from ayariety of acids beginning with the onecarbon acid (formic) through and including higher fatty acids or the equivalent having as many as 30 carbon atoms for example from 8-22 carbons.' Modified fatty acids also can be employed as, for example, phenyl stearic acid or the like. Cyclic acids may be employed, including naphthenic acids. A' variety of other acids including benzoic acid, substituted benzoic acid, alicyclic acid, and the like, have been employed to furnish the residue 1 from the acid RCOOH in which the C of the residue IRE- oic acids, for example, petrosilenic acid, oleic acid, elidic acid, the nonadecenoic acids, for example, the eicosenoic acids, the docosenoic acids, for example, erucic acid, brassidic acid, cetoleic acid, the tetracosenic acids, and the like.

Examples of dienoic acids comprise the pentadienoic acids, the hexadienoic acids, for example, sorbic acid, the octadienoic acids, for example, linoleic, and the like.

Examples ofthe trienoic acids comprise the octadecatrienoic acids, for example, linolenic acid, eleostearic acid, pseudo-eleostearic acid, and the like. i I

Carboxylic acids containing functional groups such as hydroxy groups can be employed. Hydroxy acids, particularly the alpha hydroxy acids, comprise glycolic acid, lactic acid, thehydroxyvaleric acids, the hydroxy caproic acids, the hydroxyheptanoic acids, the hydroxy caprylic 'acids,the hydroxynonanoic acids, the hydroxycapric acids, the hydroxydecanoic acids, the hydroxy lauric acids, the

: hydroxy tridecanoic acids, the hydroxymyristic acids, the

hydroxypentadecanoic' acids, the hydroxypalmitic acids, the hydroxyhexadecanoic acids, the hydroxyheptadecanoic acids, the hydroxy stearic acids, the hydroxyoctadecenoic acids, for example, ricinoleic acid, ricinelaidic acid, hydroxyoctadecynoic acids, for example, ricin is partv ofthe ring. The fatty acids employed, forqex ample, may be saturated or unsaturated. They may be hydroxylated or nonhydroxylated. Branched long chain fatty acids may be employed. See J. Am. Chem. Soc. 74, 2523 (152 This applies also to the lower molecular weight acids as well. e v

A Among sources of such acids may be mentioned straight chain and'branched chain, saturated and unsaturated, aliphatic, cycloaliphatic, aromatic, hydroaromatic, aralkyl acids,etc. H

7 Examples of saturated aliphatic monocarboxylic acids compn'ser acetic, propionic, butyric, 'valeric, caproic, heptanoic, caprylic, nonanoic, capric,'undecanoic,' lauric, tridecanoic, -:hyristic-, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, -eicosanoic,- *heneicosanoic, docosanoic, tricosanoic, tetracosanoic, pentacosanoic,

cerotic, heptacosanoic, montanic, nonacosanoic, melissic andthelike. M

Examples of ethylenic unsaturated aliphatic acids comprise; acrylic, methacryliacrotonic, .anglic, teglic,-the pentenoic acids, thehexenoic acids, for example, hydrosorbic acid, the heptenoic acids, the octcnoicacids, the nonenoic acids, the decenoic acids, for example, obtusilic acidfthe undec enoic acids, the dodencenoic acids, for example, laur'oleic, linderic, etc., the tridecenoic acids, the tetradecenoic'acids, for examplef'r'nyristoleic acid, the

stearolic acid, the hydroxyeicosanoic acids, for example, hydroxyarachidic acid, the hydroxydocosanoic acids, for example, hydroxybehenic acid, and thelike.

Examples of acetylated hydroxy acids comprise ricinoleyl lactic acid, acetyl 'ricin'ole'ic acid, chloroacetyl ricin- Oleic acid, and the, like.' 7

Examples of the cyclic aliphatic carboxylic acids com prise those found in petroleumcalled naphthenic acids, hydnocarbic and chaumoogric acids, cyclopentane carboxylic acids, cyclohexanecarboxylic acid, campholic acid, fencholic acids, and the like.

Examples of aromatic monocarboxylic. acids comprise benzoic acid, substituted benzoic acids for example, the

- toluic acids, the xyleneoic-acids, alkoxy benzoic acid,

phenyl benzoic acid, naphthalene carboxylic acid, and the like. g

' Mixed higher fatty acids derived from animal or vegetable sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil,olive oil, corn oi, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils are advantageously employed.

' Fatty and similar acids include those derived from various waxes, such as beeswax, spermaceti, montan' wax, Japan wax, coccerin and camauba wax. Such acids include oarnaubic acid, cerotic acid, lacceric acid, montanic acid, psyllastearic acid, etc. Onemay also employ higher molecular Weight carboxylic acids derived by-- oxidation and other methods, such as from paraflin wax, petroleum and similar hydrocarbons; resim'c and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid; aralkyl and aromatic acids, such as Twitchell fatty acids, naphthoic acid, carboxydiphenyl pyridine carboxylic acid. blown oils, blown oil fatty acids and the like.

pentadecenoic acids, the hexadecenoic acids, for example,

palmitoleic acid, the heptadecenoic acids, the Octodecen Other suitable acids include phenylstearic acid, benzoylnonylic acid, cetyloxybutyric acid, cetyloxyacetic acid, chlorstearic acid, etcr Examples of the polycarboxylic acids comprise those of the aliphatic series, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic acid,'decanedicarboxylic acids, undecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids comprise fumaric, maleic, mesoconic, citraconic, glutonic, itaconic, muconic, aconitic'acids, and the like.

Examples of aromatic polycarboxylic acids comprise N25 phthalic, isophthalic acids, terephthalic acids, substituted derivatives thereof (e.g. alkyl, chloro, alkoxy, etc. derivatives), biphenyldicarboxylic acid, diphenylether dicarboxylic acids, diphenylsulfone dicarboxylic acids and the like.

Higher aromatic polycarboxylic acids containing more than two .carboxylic groups comprise hemimellitic, trimellitic, trimesic, melloph'anic," prehnitic, .pyromellitic acids, mellitic acid, and the like. 1 1

Other polycarboxylic acids comprise the dimeric, trimeric and poly acids, for example, the Emery Industries polymeric acids such as those described in US. Patent 2,263,612, and the like. Other polycarboxylic acids comprise those containing ether groups, for example, diglycollic acid. Mixtures of the above acids can be advantageously employed.

In addition, acid precursors such as esters, acid chlorides, glycerides, etc. can be employed in place of the free acid.

Where the acid contains functional groups such as hydroxy groups, this should be taken into consideration in subsequent acylation in calculating the stoichiometry of acylating the hydroxyaliphatic cyclic amidine.

Hydroxy substituted imidazolines and .tetrahydropyrimidines are obtained in the manner described above from a wide variety of polyamine s containing hydroxy groups. Thus, where one starts with a polyarnine for example, a diamine -of the following formula where R is H or an alkyl group. Among the alkylene oxides that may be employed are ethylene, propylene, butylene, octylene, etc. oxides, etc. Other oxyalkylation agents such as glycide, epichlorohydrin, etc., can be employed.

Thus, compounds, within the scope of this invention which react with polycarboxylic acids comprise compoundsof the .formulae:

where REL is the residue derived fromthe carboxylic acid, where R is a. hydrocarbon radical having, for example, up to about 30 carbon-atoms such as 1-30 carbon atoms, and hydrocarbons in which thecarbon atom chain'is interrupted by oxygen, etc., It is 2 or 3, and B is a hydrogen or a hydrocarbon radical, for example, a lower alkyl radical; and D is aihydroxwaliphatic radical, for example, or R I -R)K H lz llt e nv 91. 5. a whole number, for example, 1 10 or more but preferably 1-5 and CI-I is for example, a-diveflent-radical of the formula: CH,--CH '--CHg-"CH -C" Hz-,

etc- 7 V w In general, the hydroxyalkyl cyclic amidines are prepared by reacting a polyamine containing a terminal alkanol group with a carboxylic acid at temperatures of from 150475 C. employing a zeotroping agent such as xylene to removeYwater. The reaction time of 3-4 hours is employed. Completion of reaction is judged .by the separation of .2 ,moles of H 0 .for .eachcarboxylic acid. g oup.- The products .in- ,generalare ,dark viscous oil QS ince the preparationot cyclic amidines is so well known ,(see above. cited patents) is not believed that auyexamplesare necessary to illustrate such .a well known procedure, However, for purposes of illustration the following examples are..,included.

i l i mp el l A solution of lmole of hydroxyethyl ethylene diamine,

HOCHgCHzlTTCHzCHzNHz I H U and 1 mole of oleic acid in 300 grams of xylene are charged to a flask and brought to reflux, the mixture being heated under a Dean-Stark water trap condenser in order to distill olf thefwaterwxyl'ene azeotrope mixture, separate the water and to continuously return xylene to the reaction mixture. Reflux is continued at a temperature of -170 C. for about 3 /2 hours until about 2 moles of water are removed.- The product is CHz-CH N N-CHzCHzOH v Example 9b The "above example is repeated except that hydroxyethyl propylene-dianfine 1-3;. 1

i HOCH2CH2N-OH2CHtCHZNHI is employed in place of hydroxyethylethylene diamine and stearic acid is employed in place of oleic acid. The product is /Cg2 v 20H:

N N-OHIOHIOH Example 4c Example 10a is repeated except that nocnicnigonto H'tNHi (2 moles) and a polycarboxylic acid, sebacic acid (1 mole), are employed. Instead of two moles of water being removed, as in the prior example, 4 moles of water are removed. The product is v I 7 I -v 1 i I I ExampleZUd amass me i h (2 males) and the polycarboxylic acid is terephthalic acid (1 mole). As in the prior example, 4 moles of water are removed. The product is I In general, to form the polyoxyalkylated hydroxy cyclic amidines, the hydroxyalkylcyclic, amidine is first prepared in the mannershown above and then reacted with alkylene oxides by the conventional manner of oxyalkylation to the desired; degreefof oxyalkylation using a jacketed stainless steel autoclave in the manner described in US. Patent 2,792,369. The following examples are illustrative:

1. A compound containing at least one free carboxylic acid group formed by' reacting a compound having the formula r I lo lo 1. Example 11a One mole of I 7 1L N-CH|CH2OH (50% solution in xylene) is reacted with 1 mole of ethylene oxide at a temperature of 125-130" C. and a pressure of 10-15 psi The time regulator is set to add ethylene oxide over /2 hour followed'by additional stirring for another/V2 hour to insure complete reaction. Ethylene oxide is readily taken up by the reactants. The product is cu -0H,

N N-CHzCHIOCHflCHIOH C I I v Example 12a The above example is repeated using a propylene oxide and under similar conditions. 'The product is QErCH: CHa OH:

Necmcmo 01215011101 1 Example 11a is repeated except that 2 moles of ethylene oxide are employed. The product is The above examples are :typic al methods of. preparation.

The following hydroxycyclic amidinesnrefprepared by 0 these methods.

TABLE I ROOOH some oi RC I ti %-tert-Buty1 benzoic leic V B-methoxybenzore Naphthenic TABLE II THEPOLYCARBOXYLIC ACIDS The polycarboxylic acid employed to react with the hydroxycyclicamidinecan be' varied widely. In general, they can 'be expressed as .10 1 Examples of unsaturated aliphatic polycarboxylicaeids icompni'sefumaric,-maleic, mesocenic, eitracqnie, glutonic, itaconic, mucdnic, gacohitic acids, andyth e;

Examples of aromatic polycarboxylic acids comprise phthalic, isophthaliciatfids; terephthalic acids, substituted derivatives thereof (e g. alkyl, vchloro, alkoxy, etc. derivatives), biphenyldicar-boxylic acid, 'dipheiiylether dicarboxylic acids, diphe'nylsulfone dicarboxylic acid-sand the like. l I Higher aromatic ,polycarboxylic acids containing'morle than two carboxylicgroups comprise hemi'mellitic, mellitic, trimesic," mellophanic, prehni'tic, pyromellitic acids, mellitic, acid, and the like. i

Other polycarboxylic acids comprise "the dimeric, tr-imeric and other poly acids, for example, the Emery Industries polyacids such as those disclosed in US. Patent 2,763,612, and the like. Other polycarb'oxylic acids comprise those containing ether ,groups, for example, diglycollic acid. Mixtures of the above acids can be advanta- ;geous1y'employed-. 1

:In addition, acid gprecursors such as esters, acid chlo rides, glycerides, etc. can be employed in ,:place of the free acid.

PARTIAL ESTER PRODUCTS The products of this invention are partial esters of cyclic amidines. They may be expressed by the following general formula:

wherein A comprises amolecule containing at least one cyclic amidine group having at least one ester side-chain and x is a whole number preferably 1. The

(ii-oat. of the formula indicates that the product is a partial ester having at least one free carboxylic acid group.

Thus, the product's of this invention may be 'illust'r'ated with dicarboxylic acids as follows: I

where X includes a wherein X and Zh'aveth'e meanings of the preceding iermula groups. Since the hydroxy precursor is bifunctioual (i.e., has two hydroxy groups) and the polycarboxylic acid is also polyfunctional, polyesters probably form. Since the structure is uncertain, it is indicated by dotted lines. These polyesters are useful as corrosion inhibitors pro vided they are partial esters (i.e. have at least one free carboxylic acid group) and are sufiiciently soluble in the hydrocarbon to be effective.

" j'I he: followingexamples are illustrative of the preparation of partial esters. Two moles of carboxylic acid radical are-employed for each mole of hydroxy group.

. I V ExampIeIOaA dram-01s of the product of Example 10a and 1 mole ofsebasic'acid are dissolved in 300 g. of xylene and the 're'actio'n' mixture, heated to reflux, is azeotroped, using a pean-Stark trap in the manner of Example 10a, until one l'rfnole of water is removed. The temperature is main tained at 150-l75 C. and the time is 5 hours. The prod- The process of the prior example is repeated except that terephthalic acid is employed in place of sebacic acid. The product is Example aD The above example is repeated employing 1.5 moles of CHr--CH1 N N-OHaCHaOH c 61111:: and 1 mole of trimeric acid (trilinoleic acid) to yield a dark viscous product of undetermined structure.

M Example 9bA .The process of the above example is repeated except that 1 mole of .05, r r N NCH1CH2OH I CnHar is reacted with 1 mole of adipic acid. The product is CE; l n u N N-cH,oH1o-o-(oH,)t-oorr nHis 12 and 1 mole of diglycolic acid are employed. The product 18 "(CHaCHaCDP-CHr-O-CHr- OH l C 1711a:

The above examples are typical methods of preparation. The following partial esters are prepared by these methods. Each partial ester will have the basic number shown in the prior tables, for example, la, 10a, etc., indicative of the hydroxy cyclic amidine employed. In additiong it will bear the letter A which indicates that it has been acylated to a partial ester. In each example 2 moles'of carboxylic acid radicals are employed for each mole of hydroxy groups. g I

TABLE V.--PARTI.AL ESTERS 2aB Adipic 9bB Sebacic 4aA Sebacic 9bC Terephthalic 4aB Terephthalic 9bD Succinic 10aB Adipic 21bA Sebacic v1011B Sebacic 21bB Terephthalic I 10aC Terephthalic 40A Dimeric (dilinoleic. 10aD Trimeric(trilino1eic acid) j acid) Terephthalic lOaE Succinic 60A Glutaric 13aA Sebacic 60B Pimelic 13aB Adipic 60C Adipic l5aA Suberic 14cA Adipic 1511B Dimeric acid (dilino- B Sebacic leic) 230A Sebacic 214aA Adipic 230B Isophthalic 24aB Isophthalic 23cC Adipic 28aA Diglycolic 8dA Adipic 8bA Adipic 8dB Sebacic 9bA Adipic USE AS CORROSION INHIBITOR More specifically, this phase of the invention relates to the inhibition of corrosion in the petroleum industry with specific reference to producing wells, pipe lines, refineries, tank storage, etc.

The use of a corrosion inhibiting agent in the oil. industry and other industries, and particularly for the protection of ferrous metals, isswell known. For example, see US. Patents Nos. 2,736,658, dated February 28,1954, to Pfohl et al., and 2,756,2l1,'dated July 24, 195.6,.to Jones, and 2,727,003, dated December 13, 1955, to Hughes. i l s I More specifically then, and particularly from the standpoint of oil production, this aspectof the invention relates to inhibiting corrosion caused by hydrogen sulfide, carbon dioxide, inorganic and organic acids, combinations of each with oxygen, and with each other and oxygen. More particularly, it relates to. treating wellsto mitigate metal corrosion and associated difliculties. 1

It should also be pointed out that the corrosivness of oil well brines will vary from well to well, and the proportion of corrosion inhibiting agent added .to the well fluids-should also be varied from well to well. Thus, in some wells it is possible to effectively control corrosion 'by the addition of as little as 5 ppm. ofour new compositions to the well fluids, whereas in other wells, it is necesary to add 200 ppm. or more.

In using our improved compositions for protecting oil well tubing, casing and other equipment which comes in contact with the corrosive oil-brine production, we find that excellent results may be obtained by injecting an appropriate quantity, of a selected composition into a producing well so that it mingles with the oil-brine mixture and come into contact with the casing, tubing, pumps and other producing equipment. We, for example, can introduce the inhibiting composition into the top of the casing, thus causing it to flow. down into the well and the inhibitor is somewhat surface-active; concentrated at interfacial' surfaces.

13 thence back through the tubingetc; In general, we have foundthat this procedure suflices to inhibit corrosion thfo'ugh'out the entire system of production, and collection, even including field tankage.

In case serious emulsion or gel problems are encountered, deniulsifi'e'rs are advantageously added. This is important not only to avoid the tioublm'ome emulsions and gels themselves, but also to improve corrosion inhibition. The explanation of less effective corrosion inhibition in the presence of emulsions apparently is that That is, it is Since this surface is great in an emulsion, most of the inhibitor will be concentrated in these interfaces and little will remain in the body of the oil for deposition on the metal surfaces. In many wells, oil-in-water type emulsions often occur naturally. In such wells the inhibitors herein described tending to form water-in-oil type emulsions, often decrease the emulsion problems naturally present. Thus, in addition to being effective corrosion inhibitors, the herein described products tend to eliminate emulsion problems which sometimes appear when some of the present day inhibitors are used in oil wells or refinery processing.

The method of carrying out our process is relatively simple in principle. The corrosion preventive reagent-is dissolved in the liquid corrosive medium in small amounts and is thus kept in contact with the metal surface to be protected. Alternatively, the corrosion inhibitor may be applied first to the metal surface, either as is, or as a solution in some carrier liquid or paste. Continuous application, as in the corrosive solution, is the preferred method, however.

The present process finds particular utility in the protectionof metal equipment of oil and gas wells, especially those containing or producing an acidic constituent such as H 8, CO inorganic and organic acids, and the like. For the protection of such wells, the reagent, either undiluted or dissolved in a suitable solvent, is fed down the annulus of the well between the casing and producing tubing where it becomes commingled with the "fluid in the well and is pumped or flowed from the well with these fluids, thus contacting the inner wall 'of the casing, the outer and inner wall of tubing, and the inner surface of all well-head fittings, connections and flow lines handling the corrosive fluid.

Where the inhibitor composition is a liquid, it is conver'rtionally fed into the well annulus by means of a motor driven'chemical injector pump, or it may be dumped periodically (e.g., once every day or two) into the annulus by means of a so-called boll weevil device or similar arrangement. Where the inhibitor is a solid, it is dropped into the well as a solid lump or stick, blown in as a powder with gas, or it may be washed in with -a small stream of the well fluids or other liquid. Where there is gas pressure on the casing, it is necessary, of course, to employ any of these treating methods through a pressure equalizing chamber equipped to allow introduction of reagent into the chamber, equalization of pressure between chamber and casing, and travel of reagent from chamber to well casing.

Occasionally, oil and gas wells are completed in such a manner that there is no opening between the annulus and the bottom of the tubing or pump. This results, for example, when the tubing is surrounded at some point by a packing held by the casing or earth formation below the casing. In such wells the reagent may be introduced into the tubing through a pressure equalizing Vessel, after stopping the flow of fluids. After being so treated, the well should be left closed in for a period of time sufiicient to permit the reagent to drop to the bottom of the well.

For injection into the well annulus, the corrosion inhibitor is usually employed as a solution in a suitable solvent, such as mineral oil, methylethyl ketone, xylene, kerosene, or even water. The selection of solvent will depend 14 ranch upon :the exactreagent being used and its solubility characteristics. It is also generally desirable to employ "a solvent whieh'w' il-l yield a solutiono'flow nee'zing so "as to eev the necessity er neatingfthe ale on and injection equipment du-rmgwinter "use. 1

For treating wells with packed-elf tubing, tueus'e 6f solid sticks or plugs of inhibitor is especially convenient. These are prepared by blending the inhibitor with a mineral wax, asphalt or resin in a proportion sufficient to give a moderatelyha'rd and hig'h m'elting solid which can be handled and fed into the well conveniently.

The amount of corrosion preventive jagerit required in our process varies with the corrosiveness of the system, but where a continuous for semi-continuous treating procedure is carried out as described above, the addition of reagent in the proportion of from 3 parts per million to 1000 parts per million or rnoreparts of corrosive fluid will generally provide protection.

These corrosion inhibitors can be used in combination with other well-known corrosion inhibitors, for example, the cyclic amidine structures, the amide ciyclic amidine structures, and the amino cyclic amidines structures, as

disclosed in "the Blair and Gross Reissue Patent No. 23,227. When the herein described products are mixed with corrosion inhibitors of the onventional type in the ratio of on'e to-th'ree, one to one, three to-one, or the like, in numerous instances the effectiveness of the corrosion inhibitor thus obtained is often significantly greater than 'the'usef either one alone.

Since these products are basic they can be combined with various acids to producesalts in which oil solubility is increased or decreased. Likewise, water solubility is increased or decreased. For instance, the products are mixed with one or more moles of an acid, such as higher fatty acids, 'dimerized fatty acids, naphthenie acids, fafcids obtained by the oxidation of hydrocarbons, as Well as sulfonic acids such as dodecylbenzene sulfonic acid, petroleum mahogany acids, petroleum green acids, etc.

What has been said in regard to the acids which -increase oil solubility and decrease water solubility applies with "equal force and effect to acids of the type, such as acetic acid, hydroxyacetic acids, gluconic acid, etc., all of which obviously introduce hydrophile character when they form salts or complexes, if complexes are formed. For example, any of the acids described above in preparing the cyclic amidines are useful in preparing these salts.

As pointed out previously, the addition of corrosion inhibitors, particularly'inthefornrof a-solution'by means'of a metering pump or the like, is common practice. "The particular corrosion inhibitors herein described are applied in the same manner as other conrosion inhibitors intended for use for the same purpose. For sake of brevity, as to the use of the corrosion-inhibitor and its solution in a suitable solvent such as mineral oil, methyl ethyl ketone, xylene, kerosene, high boiling aromatic solvent, or-even water.

STnuuNo TESTS These tests are run on synthetic fluids. The procedure involves the comparison of the amount of iron :in solution after a predetermined interval of time of contact of 'a standardized iron surface with a two-phase corrosive medium with similar determinations in systems'containing inhibitors.

hundred ml. beakers equipped with stirrers and heaters are "changedwith 400 ml. :of 10% sodium chloride-containing 500 p:p.1n. acetic acid and -ml. "of mineral spirits. The liquids are brought to temperature and a 1 'x 1 1n hsa'n'd blasted coupon is suspended bymeans of aglass hook approximately midway into the liquid phase of thefbeaker.v T he stirrer is adjusted to agitate-the liquids as such'arate as-to-providegood mixing of thetwo layers.

After 30 inmates samples of the aqueous phase are taken and the ironcontent of eachsample is determined by measuring the color termed "by the addition of hydrochloric acid and potassium thiocyanate in a' photoelectric colorimeter. I

The protection aiforded by an inhibitor. is measured by comparison of the amount of light absorbed by inhibited '1 6 The unexpectedness of the invention is quite evident from the above data. The products of the present invention are superior to both the unesterified imidazoline and to other commercial inhibitors containing the 'imidazoline and uninhibited samples run simultaneously. Percent 5 structure. The commercial inhibitors with which the protection can be determined by the following formula: partial esters were compared were those chosen for A2 V standards of excellent performance. X 100 r percent protection where A is the present light absorbed by an uninhibited V O R USES Sample and 2 is Q Same Value for an illhibited if These products are effective not only as corrosion I Resums of a WP 11111 are Set fOfth 111 the followlng inhibitors but can be used for a number of other pur- .table: poses. For instance, they are useful as asphalt additives TABLE VI to increase the adhesiveness of the asphalt to the mineral CHECH, aggregates. In the form of water soluble salts, they are useful as bactericides in the secondary recovery of oil. The hydroxycyclic amidine may be subjected to extensive C oxyalkylation by means of ethylene oxide, propylene oxide, butylene oxide, or the like prior to acylation. 20 These are oxyalkylated and still have oil solubility as, for Stirring Test at Room example, by the addition of propylene oxide or butylene Inhibitor g iigg ggggg ggg oxide, or are oxyalkylated to produce water solubility as, Ex gg l ti 53 b se on for example, by means of ethylene oxide, glycide, etc. They are also oxyalkylated by combinations of propylene R M1 d Wgt Loss Percent oxide and ethylene oxide so that both water solubility M Protection and oil solubility remain. Thereupon they are reacted with polycarboxylic acids. Such products are useful for 1022, a variety of purposes and particularly for those where 99 nonionic surfactants or sequestered cationic surfactants 0.6 99 99 are mdrcated. A 32' In addition, the compounds of this invention have the 0,,11,, 4 23 following applications: 883E333 Inhibitor B g3 g8 AgricuIturer-Additive for kerosene, use in phenothi- 35 azine and pyrethrum sprays, as fungicides, herb cidal oils. 1 The unesterifled amine. Ann-static treatment.-For hotel rugs, hospital floors, -m analysis indicates imidamune structmeautomobile upholstery, plastic and Wax polishes, wool TABLE VII oils, lubricants for synthetic fibers.

[stirring test at 40 Buzldmg materzals.Water repellent treatment for 40 plaster, concrete, cement, roofing materlals, air entrain- Inhibitor ment, floor sealers, linoleum. i gg gg g Cosmetics.--Formulation of anti-perspirants, deodor- R Acid ants, sun screens, hair preparations. De-emulsifying.-In antibiotic extraction, breaking 100B gngnw. g ebacifiunffnn g crude oil and water-gas for emulsions. 13GB 3 11: gf ff ff 97 Detergents.Metal cleaning emulsions, lens cleaners, Y I Ci1Haa-- None} 9 floor oils, dry cleaning detergents, radiator flushes, cess- Commerclal Inh 81 pool acid, boiler scale solvents, germicidal corrosion- It has been noted that some compounds have a definite actuation inhibited acid detergents for dairies, enamel q p "energy so these tests are often run at room temperature as well as at t il t b w1 tltftiififigififis Leather.Flat liquoring oils, pickling acid degreasing, I Infra-red indicates imldazoline structure. d fi ti v 'T KE T T (C T Metals.Rust preventive oils, cutting oils, Water dis- This test was described by Malcolmson et a1. (Annual Placing un pickling inhibitor, Solvent degreasipg- Meeting of the Society of Naval Architects and Marine 5 Improved adhtislofl P pfevenilng Engineers, New York, November 1952 It involves Water Spottmg 1n lacquers, p g ay s flushme the measurement by weight loss of coupons which have grinding and dispersmg, almefeathenng 111 been subjected to the corrosive action of sea Water and Petmleum--U$e as germicide in flood water treat a hydrocarbon for a week followed by contact for one y g fuel Oil additives, l agent week with sea water and air, and the composition there in asphalt emulsions and cutbacks- -to the-weight loss of coupons subjected to a similar test Textiles.In rubberizing, textile oils, dyeing assistants, in which a small amount or inhibitor has been added to fteningagents. the hydrocarbon phase. I M iscellan'eous.Bentonite-amine complexes, metal- TABLE vIIL-TANKER TEST (CYCLE TEST) Inhibitor. Wgt. Loss, Mg. Percent Protection as. l

' R Acid 10 20 30 10 20 30 p.p.m. p.p.m. p.p.m. p.p.m. p.p.m. p.p.m.

10110-. 0111133"-.. Terephthalic 11.0 9.5 11.7 72.5 76.0 76.0 134113-- 017113,--. Adipic 11.8 12.8 18.2 66.2 68.0 54.5 Commercial Inhibitor O 21.2 19.6 20.0 50.0 52.5 s 53.0 OnHss, Free Alcohol, Wgt. Less p.p.m.) 200.6, Percent Protection (100 ppm.) 4 5 Infra-red indicates imidaz oline structure.

R-(( lH), where R' is hydrocarbon having 1-36 carbon atoms.

2. A compound containing free carboxylic acid group formed by reacting a compound having the formula A03 AOH 18 where R is hydrocarbon having 1-36 carbon atoms, and A is lower alkylene having at least two carbon atoms, with at least one mole of a polycarboxylic acid having the formula where R is hydrocarbon having 1-36 carbon atoms. 3. A compound formed by reacting one mole of GET-{3H2 CH CHz HOCHflCHfl-N N N N-CHaCHzOH C(CHz)a-C with two moles of dilinoleic acid.

References Cited in the file of this patent UNITED STATES PATENTS 2,211,011 Chwala Aug. 13, 1940 2,267,965 Wilson Sept. 30, 1941 2,324,491 De Groote et a1 July 20, 1943 2,369,818 De Groote et a1. Feb. 20, 1945 2,468,163 Blair et a1. Apr. 26, 1949 2,468,180 De Groote et a1. Apr. 26, 1949 2,574,537 De Groote et al Nov. 13, 1951 2,640,029 Blair et a1 May 26, 1953 2,695,884 Smith Nov. 30, 1954 2,713,559 Smith July 19, 1955 2,713,582 Smith July 19, 1955 2,773,879 Sterlin Dec. 11, 1956 2,845,439 Grant et a1. July 29, 1958 

1. A COMPOUND CONTAINING AT LEAST ONE FREE CARBOXYLIC ACID GROUP FORMED BY REACTING A COMPOUND HAVING THE FORMULA 